Curable epoxy resin compositions containing water-processable polyamine hardeners

ABSTRACT

A curable composition is described, comprising a) 10 to 90% by weight of at least one, optionally water-dilutable, water-emulsifiable or water-dispersible, epoxy resin having more than one epoxy group in the molecule; b) 90 to 10% by weight of at least one polyamine adduct which predominantly corresponds to the idealised formula (I) and which is prepared from an adduct of formula (A) and a polyamine of formula (XII), wherein the sum of the percentages by weight of components (a) and (b) is always 100%; c) optionally, at least one further aliphatic, cycloaliphatic, aromatic/aliphatic, aromatic or heteroaromatic mono- or polyamine which may optionally be modified by adduction; and d) optionally, at least one customary additive, R 1  and R 2  and also m and n and B being defined in more detail in the description. The novel compositions are used for the preparation of colourants and coatings.

The present invention relates to curable compositions comprising anepoxy resin and specific water-processable polyamine hardeners andoptional further customary additives, to the use thereof for thepreparation of moulded articles, in particular of coatings, as well asto the cured moulded articles and coatings, and also to specificpolyamine hardeners.

Polyamidoamines, which contain free amino groups and which can beprepared from polyalkylene polyamines and polymerised unsaturatednatural fatty acids, can be used for curing epoxy resins [see Lee &Neville “Handbook of Epoxy Resins”, McGraw-Hill Book Co., New York 1967,chapter 10, pages 1-12]. U.S. Pat. No. 3,280,054 discloses that it ispossible to cure epoxy resins, in the absence of water, with adductswhich are formed from polyamidoamines and polyepoxides.

German Offenlegungsschrift 1 520 918 proposes to use exactly theseadducts and epoxy resins to prepare curable aqueous dispersions. It hasbeen found, however, that the products so obtained often do not meet therequirements; in some cases, for example, the adducts, in particular theadducts prepared from aromatic polyepoxides, are semi-solid and aretherefore not completely dispersible in aqueous medium, while aqueousdispersions comprising an aromatic epoxy resin and an adduct preparedfrom an aliphatic polyepoxide often show undesirable thixotropicbehaviour. U.S. Pat. No. 3,383,347 proposes using phenol-modified aminesas curing agents, which can be obtained as reaction products of aprimary amino group of an aliphatic polyamine with a phenol and, whereappropriate, of an aldehyde. However, the epoxy resin hardener emulsionsobtained therewith have a short processing time and give very brittlecoatings.

German Offenlegungsschrift 1 925 941 discloses epoxy resin hardeneremulsions which comprise as hardener component an aminoamide adduct ofan aminoamide consisting of an alkylene polyamine and a fatty acid.These emulsions are instable and often precipitate water already duringthe processing period. The relatively soft coatings prepared therefromare susceptible to mechanical stress and are therefore unsuitable forthe preparation of resistant protective coatings.

Swiss patent 487 955 proposes the use of aqueous dispersions whichpreferably additionally contain an accelerator for curing. The coatingsprepared therewith are also relatively soft and are therefore onlylimitedly suited to, inter alia, mechanical stress.

Associates, consisting of a polyamidoamine adduct having astoichiometric excess of a polyamidoamine, of an aliphatic epoxycompound and of a phenol/formaldehyde polyamine condensate, are proposedas curing agents for aqueous epoxy resin dispersions in GermanOffenlegungschrift 2 332 177. However, organic water-dilutable solventsmust be added to this mixture of epoxy resin prepolymer and curing agentto permit, by reducing the viscosity, their use as coating compound.Many organic solvents, however, carry risks known to the skilled person,such as inflammability, toxicity, environmental pollution, and the like.

In 2- or 3-component systems with epoxy resins, the working life ofpolyamine-terminated water-based polyamine hardeners, such as thosedescribed in U.S. Pat. No. 4,197,389, is usually too short. This can beremedied by reacting the polyamine-terminated curing component furtherwith monofunctional amine-reactive compounds, for example withacrylonitrile, aliphatic or araliphatic monoepoxy compounds ormonocarboxylic acids; and the salt formation of the polyamine adductswith inorganic or organic acids, such as acetic acid, which convert thepolyamine adduct into a cationic and therefore water-dilutable form, mayalso be advantageous. [See U.S. Pat. Nos. 4,093,594; 4,246,148;4,539,347 and 4,608,405]. However, both processing methods havedisadvantages: The reaction of the polyamine adducts with reactivecomponents results in a loss of NH-active hydrogen atoms and thus in anexcess consumption of hardener. At the same time, the thermal stabilityof the hardener formulation decreases, i.e. at temperatures above 40° C.phase separation almost always occurs. Owing to the remaining ammoniumsalts, the reaction of polyamines with acids results in an increasedcorrosion tendency as well as in bubble formation on the surface coatingwhich leads to a reduced stability of the chemicals.

Surprisingly, it has now been found that aqueous formulations comprisingspecific diaminocyclohexane adducts and epoxy resins have a drasticallyprolonged working life compared to formulations comprising customarypolyamine adducts such as aliphatic or cycloaliphatic amine adducts ormixtures of meta-xylylenediamine/isophoronediamine adducts. This was notto be expected, as diaminocyclohexane adduct hardeners in solvent-freesystems do not show this prolonged working life effect.

Accordingly, this invention relates to curable compositions comprising:

a) 10 to 90% by weight of at least one, optionally water-dilutable,water-emulsifiable or water-dispersible, epoxy resin having more thanone epoxy group in the molecule, and

b) 90 to 10% by weight of at least one polyamine adduct whichpredominantly corresponds to the idealised formula I and which isprepared from an adduct of formula A and a polyamine of formula XII,

wherein the sum of the percentages by weight of components a) and b) is100%,

c) optionally, at least one further aliphatic, cycloaliphatic,aromatic/aliphatic, aromatic or heteroaromatic mono- or polyamine whichmay be modified by adduction, or mixtures thereof, and,

d) optionally, at least one customary additive,

wherein in formulae I or A and XII

R¹ is independently of one another —H or —CH₃,

R² is —H or C₁-C₁₂alkyl, and

p is 1, 2 or 3,

the radicals B are each independently of one another a group of formulaeII, III, IV, V, VI, VII, VIII, IX and X:

wherein

X is >N— or —O—,

R is —H or —CH₃, and

q is an integer from 0 to 10,

m in formulae I and A, depending on the functionality of unit B, is aninteger from 1 to 11, and

n is an integer from 2 to 100, and

r in formulae VI and VII is an integer from 2 to 20.

Preferred ratios of components a) and b) are 40 to 90% by weight ofcomponent a) to 60 to 10% by weight of component b). Component c) isconveniently used in an amount of at most 30 % by weight, preferablyfrom 5 to 20% by weight, based on component b).

If R¹ in formulae I and A is different substitutents, then the compoundsof formulae I and A are randomly distributed or grouped blockwise.

In formulae II, III, IV and V, the phenyl radicals can also besubstituted by C₁-C₁₂alkyl or halogen atoms, preferably chloro or bromo.

In contradistinction to known compositions, e.g. those based onisophoronediamine/meta-xylyienediamine, the compositions of thisinvention with water-based epoxy resins have, at comparable NH-activeequivalent weight (HAV for short), a substantially prolonged workinglife while having comparable curing properties. Surprisingly, it is inthis case possible to forego further modification of the novelcompositions by adduction or reaction with organic acids.

It has also been found that in a synergistic blend with specific metalsalts, the novel compositions react faster, even in the presence ofgreat amounts of water, while no, or hardly any, acceleration effectsare found in solvent-free systems based on diaminocyciohexanes.Furthermore, it has been found that, surprisingly, the working life ofthe composition is not reduced in contrast to that of solvent-freesystems containing accelerators.

The novel polyamine hardener component b) can usefully also beadditionally modified by partially blending the component b) with areaction product consisting of an adduct of the above formula A with amonoalkyl ether, e.g. ethylcarbitol, or with a secondary amine, such asdi-n-butylamine, such that the viscosity of the novel adduct can beadjusted or reduced as desired. Component b) conveniently comprises upto 20 mol % of the component b) modified in this manner.

The monoalkyl ether conforms to formula XIII

wherein

t is an integer from 2 to 4,

s is an integer from 1 to 5, and

R³ is C₁-C₆alkyl, C₆-C₁₀aryl or C₇-C₁₁aralkyl.

Preferred compounds are those of formula XIII, wherein

t is an integer from 2 to 3,

s is an integer from 1 to 4, and

R³ is C₁-C₆alkyl or C₆-C₁₀aryl.

Particularly preferred compounds are those of formula XIII, wherein

t is an integer from 2 to 3,

s is an integer from 1 to 3, and

R³ is C₁-C₆alkyl.

Monoalkyl ethers of formula (XIII) are very particularly preferablypolyethylene glycol monoalkyl ethers, polypropylene glycol monoalkylethers and polybutylene glycol monoalkyl ethers, in particularpolyethylene glycol monoalkyl ether and polypropylene glycol monoalkylether, more preferably polyethylene glycol monomethyl ether,polypropylene glycol monomethyl ether, polyethylene glycol monoethylether and polypropylene glycol monoethyl ether. Diethylene glycolmonoethyl ether (=ethylcarbitol) is very particularly preferred.

Suitable secondary amines have the general formula XIV:

wherein R⁴ and R⁵ are each independently of the other C₁-C₁₈alkyl,C₆-C₁₀aryl, C₇-C₁₁aralkyl or, taken together, —(CH₂)₄—, —(CH₂)₅— or—(CH₂)₂—O—(CH₂)₂—

The secondary amines may additionally be functionalised, e.g. withhydroxyl groups; a typical example is diethanolamine.

Particularly preferred compounds are those of formula XIV, wherein R⁴and R5 are each independently of the other C₁-C₁₀alkyl or C₆-C₁₀aryl.

Very particularly preferred compounds are those of formula XIV, whereinR⁴ and R⁵ are each independently of the other C₁-C₆alkyl, but preferablydi-n-butylamine, di(n-propyl)amine, di(isopropyl)amine anddi(isobutyl)amine.

Mixtures of the above monoalkyl ethers or of the secondary amines canalso be used.

Alkyl containing up to 18 carbon atoms referring to R² (up to C₁₂), R³(up to C₆), R⁴ and R⁵ in formulae XIII and XIV is a branched orstraight-chain radical, typically methyl, ethyl, propyl, isopropyl,n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl,isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl,n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl,3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethyl-hexyl,1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl,dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl or octadecyl.

R³ and R⁴/R⁵ defined as C₆-C₁₀aryl typically include phenyl,methylphenyl (tolyl), dimethylphenyl (xylyl), trimethylphenyl(mesityl),ethylphenyl, propylphenyl, butylphenyl or naphthyl.

R⁴ and R⁵ defined as C₇-C₁₁aralkyl typically include benzyl,α-methylbenzyl, α,α-dimethylbenzyl or 2-phenylethyl, 2-methylbenzyl,3-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl, 2,6-dimethylbenzylor 4-tert-butylbenzyl.

Epoxy resin a) may, in principle, be any epoxy resin customarily usedfor application.

Illustrative examples of epoxy resins used as component a) are:

I) Polyglycidyl and poly(β-methylglycidyl) esters which are obtainableby reacting a compound containing at least two carboxyl groups in themolecule and epichlorohydrin or β-methylepichlorohydrin. The reaction isconveniently carried out in the presence of a base.

Compounds containing at least two carboxyl groups in the molecule maysuitably be aliphatic polycarboxylic acids. Examples of suchpolycarboxylic acids are oxalic acid, succinic acid, glutaric acid,adipic acid, pimelic acid, suberic acid, azelaic acid or dimerised ortrimerised linoleic acid.

It is, however, also possible to use cycloaliphatic polycarboxylic acidssuch as tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid,hexahydrophthalic acid or 4-methylhexahydrophthalic acid.

Aromatic polycarboxylic acids can also be used, typically phthalic acid,isophthalic acid and terephthalic acid.

II) Polyglycidyl or poly(β-methylglycidyl)ethers which are obtainable byreacting a compound containing at least two free alcoholic hydroxylgroups and/or phenolic hydroxyl groups and epichlorohydrin orβ-methylepichlorohydrin, under alkaline conditions or in the presence ofan acid catalyst and subsequent treatment with an alkali.

The glycidyl ethers of this type are typically derived from acyclicalcohols, typically from ethylene glycol, diethylene glycol and higherpoly(oxyethylene)glycols, 1,2-propanediol or poly(oxypropylene)glycols,1,3-propanediol, 1,4-butanediol, poly(oxytetramethylene) glycols,1,5-pentanediol, 1,6-hexanediol, 2,4,6-hexanetriol, glycerol,1,1,1-trimethylolpropane, pentaerythritol, sorbitol, as well as frompolyepichlorohydrins.

They may also be derived from cycloaliphatic alcohols such as1,4-cyclohexanedimethanol, bis(4-hydroxycyclohexyl)methane or2,2-bis(4-hydroxycyclohexyl)propane, or they contain aromatic nucleisuch as N,N-bis(2-hydroxyethyl)aniline orp,p′-bis(2-hydroxyethylamino)diphenylmethane.

The glycidyl ethers may also be derived from mononuclear phenols,typically from resorcinol or hydroquinone, or they are derived frompolynuclear phenols such as bis(4-hydroxyphenyl)methane,4,4′-dihydroxybiphenyl, bis(4-hydroxyphenyl)sulfone,1,1,2,2-tetrakis-(4-hydroxyphenyl)ethane,2,2-bis(4-hydroxyphenyl)propane,2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, as well as from novolaksobtainable by condensation of aldehydes such as formaldehyde,acetaldehyde, chloral or furfuraldehyde, with phenols such as phenol, orwith phenols which are substituted in the nucleus by chlorine atoms orC₁-C₉alkyl groups, for example 4-chlorophenol, 2-methylphenol or4-tert-butylphenol, or by condensation with bisphenols of the type citedabove.

III) Poly-(N-glycidyl) compounds obtainable by dehydrochlorination ofthe reaction products of epichlorohydrin with amines which contain atleast two amino hydrogen atoms. These amines are typically aniline,n-butylamine, bis(4-aminophenyl)methane, m-xylylenediamine orbis(4-methylaminophenyl)methane. The poly(N-glycidyl) compounds alsoinclude triglycidyl isocyanurate, N,N′-diglycidyl derivatives ofcycloalkylene ureas such as ethylene urea or 1,3-propylene urea, anddiglycidyl derivatives of hydantoins, typically of5,5-dimethylhydantoin.

IV) Poly(S-glycidyl) compounds, preferably bis(S-glycidyl) derivativeswhich are derived from dithiols such as 1,2-ethanediol orbis(4-mercaptomethylphenyl)ether.

V) Cycloaliphatic epoxy resins, including bis(2,3-epoxycyclopentyl)ether, 2,3-epoxycyclopentyl glycidyl ether,1,2-bis(2,3-epoxycyclopentyloxy)ethane or3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexanecarboxylate.

It is also possible to use epoxy resins in which the 1,2-epoxy groupsare attached to different hetero atoms or functional groups. Thesecompounds typically comprise the N,N,O-triglycidyl derivative of4-aminophenol, the glycidyl ether-glycidyl ester of salicylic acid,N-glycidyl-N′-(2-glycidyloxypropyl)-5,5-dimethylhydantoin or2-glycidyloxy-1,3-bis(5,5-dimethyl-1-glycidylhydantoin-3-yl)propane.

It is preferred to use epoxy resins having an epoxy content of 1 to 10equivalents/kg, which are glycidyl ethers, glycidyl esters or N-glycidylderivatives of aromatic, heterocyclic, cycloaliphatic or aliphaticcompounds. The epoxy resins used are preferably liquid, i.e. they areeither liquid resins or liquid mixtures of solid and liquid resins, orthey are obtained as dispersions in water, if required together withsmall amounts of organic solvents.

Particularly preferred epoxy resins are polyglycidyl ethers of novolaks,more preferably of bisphenols, typically of2,2-bis(4-hydroxyphenyl)propane (bisphenol A) orbis(4-hydroxyphenyl)methane (bisphenol F).

Very particularly preferred epoxy resins are diglycidyl ethers ofbisphenol A or bisphenol F, and also epoxy novolaks.

Component b) in the novel compositions are the water-processablepolyamine hardeners of formula I, wherein the polyamine hardener issoluble in water as solvent or may be dissolved in water by the additionof small amounts of water-soluble organic solvents.

The above formula I is an idealised structural formula and correspondsto the main component of those structures which are obtained in thepreparation of these polyamine hardeners.

The compounds of formula I are prepared by per se known methods in atwo-step process where, in a first step, a polyether polyol of formulaXI

is reacted with a polyepoxide conveniently at elevated temperature tothe adduct of formula A (e.g. in accordance with EP-A-0 000 605),wherein R¹ and n have the meanings cited above.

Elevated temperature usefully means e.g. a temperature range from 120 to160° C. An epoxy compound having a molar excess from about 2 to 10 permol of polyether polyol is conveniently used. An inert organic solventmay optionally also be used.

All customary polyepoxy resins within the meaning of above formula A,e.g. aliphatic, cycloaliphatic, aromatic or heteroaromatic polyepoxyresins, can be employed for the adduction reaction. Particularlypreferred are the polyglycidyl ethers of polyvalent phenols, typicallyof 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) orbis(4-hydroxyphenyl)methane (bisphenol F) or of novolaks, or ofaliphatic polyols, preferably of straight-chain terminal diols,typically butanediol or hexanediol.

Polyether polyols of formula XI are the following conventionalcomponents of the technology (see UIImanns Encyclopädie der technischenChemie, 4. Ed., Vol. 19, Verlag Chemie GmbH, Weinheim 1980, pages 31-38and pages 304, 305). They can be obtained, for example, by reaction of astarter with alkylene oxides, typically with ethylene oxide or propyleneoxide. Suitable starters are all starters usually suitable for thepreparation of polyether polyols having a functionality of 2 to 4, forexample water, aliphatic, cycloaliphatic or aromatic polyhydroxycompounds having 2 to 4 hydroxyl groups, such as ethylene glycol,propylene glycol. Preferred polyether polyols are those based onethylene oxide and/or propylene oxide, the ethylene/propylene oxidecopolymers being randomly distributed or block copolymers. The ratio ofethylene oxide to propylene oxide can vary within wide limits. It is,for example, possible that only the terminal hydroxyl groups of thepolyether polyols are reacted with ethylene oxide (end capping). Theethylene oxide units content of the polyether polyols suitable forcomponent b) can also have values of e.g. up to 75 or 80%. It willusually be convenient for the polyether polyols to be end-capped atleast with ethylene oxide, because they will then have terminal primaryhydroxyl groups which are more reactive towards the epoxy componentsused than the secondary hydroxyl groups obtained from the reaction withpropylene oxide.

The condensate of formula A so obtained is then reacted in a second stepwith an amine of the above formula XII [optionally with the addition ofa less than stoichiometric amount of a monofunctional alcohol (monoalkylether of formula (XIII) or of a secondary amine of formula (XIV) for themodification of component b)], with heating, to the component of formulaI and, where required, the resulting mixture is diluted with water. Inthe synthesis, these compounds are usually obtained as mixtures. Thereaction may be carried out e.g. in the temperature range from 40 to120° C., optionally in the presence of an inert organic solvent. It isconvenient to use a c. 1-10-fold molar excess of diamine of formula XIIper mol of condensate A.

Typical examples of diaminocyclohexane derivatives of formula XII arethe following:

R² defined as C₁-C₁₂alkyl is typically methyl, ethyl, propyl, isopropyl,n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl,isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl,n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl,3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl,1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl,dodecyl, 1,1,3,3,5,5-hexamethylhexyl. The alkyl group R² preferablycontains 1 to 6, more preferably 1 to 4, carbon atoms. Alkyl R² isparticularly preferably methyl.

Typical examples of amines of formula XII are:

1,2-, 1,3- and 1,4-diaminocyclohexane, 1,3-diamino-2-methyl- or-4-methylcyclohexane.

The compounds of formula I are novel compounds. Preferred compounds arethose of formula I

wherein

R² is —H or —CH₃, and p is 1, and

m, depending on the functionality of unit B, is an integer from 1 to 5,and

n is an integer from 4 to 25, and B has the meanings stated above.

Of particular interest are polyamine hardeners of formula I, wherein

R² is —H, and p is 1, and

the two amino groups are in ortho-position to each other, or

R² is —CH₃, and p is 1, and

the two amino groups are in meta-position to each other,

the radicals B are independently of one another a group of formulae II,III, IV and V

or of formula VI —O—(CH₂)_(r)—O—, wherein r is an integer from 2 to 10,and R and q have the meanings stated above.

Of very particular interest are polyamine hardeners of formula I,wherein

R² is —H, and p is 1, and

the two amino groups are in ortho-position to each other, and

the radicals B have the meaning stated above,

q in formula V being 0 to 3, and r in formula VI being 4 or 6.

Examples of processes for the preparation of the novel polyaminehardeners in accordance with formula I are discussed in the experimentalpart.

As mentioned above, the novel compositions may comprise as furthercomponent c) additives of aliphatic, cycloaliphatic, aromatic/aliphatic,aromatic or heteroaromatic mono- or polyamines. These added amines serveto modify the performance properties of the novel polyamine adducts offormula I. For example, the reactivity/working life profile of the novelhardeners as compared to the epoxy resin component a) can be adjusted bythe addition of more reactive polyamines to the adduct of formula I.Most conveniently, the additional amines are added after the adductingreaction of adduct A (polyepoxy/polyether polyol) and of thediaminocyclohexane derivative of formula XII is complete and beforewater is added to the novel component b). This process is exemplified inthe experimental part.

Mono- or polyamines which may optionally be modified by adduction are,for example, reaction products with monoepoxy resins, Michaelcondensates addition products using unsaturated compounds, typicallyacrylonitrile, or reaction products of the mono- or polyamines withmonocarboxylic acids.

Illustrative examples of mono- and polyamines as component c) are:

ethylenediamine, 1,2- and 1,3-propylenediamine,2-methyl-1,5-diaminopentane (DYTEK-A®, DuPont), hexamethylenediamine,N-aminoethylethanolamine, diethylenetriamine, triethylenetetramine,tetraethylenepentadiamine, dipropylenetriamine,2,2,4-trimethyl-1,6-diaminohexane, meta-xylylenediamine,N-2-aminoethylpiperazine,2,5(2,6)-bis(aminomethyl)bicyclo(2.2.1)heptane,bis(4-amino-3-methylcyclohexyl)methane, bis(4-aminocyclohexyl)methane,1,3-diamino-4-methylcyclohexane, 1,2-diaminecyclohexane,4,4′-diaminodiphenylmethane.

The amount of component d) depends on the respective embodiment of thisinvention and can therefore be completely variable, e.g. from 0 to 98%by weight, based on the total weight of components a), b), c) and d).

Illustrative examples of additional additives used as component d), someof which are commercially available, are the following:

Extenders, fillers, reinforcing agents, such as coal tar, bitumen,textile fibres, glass fibres, asbestos fibres, boron fibres, carbonfibres, mineral silicates, mica, quartz powder, aluminium oxide hydrate,bentonite, wollastonite, kaolin, silica aerogel or metal powders, e.g.aluminium powder or iron powder, and also pigments or pigment pastes,and colourants, such as carbon black, oxide colours and titaniumdioxide, flame retardants, thixotropic agents, flow control agents, suchas silicones, waxes and stearates, some of which are also used asdemoulding agents; antifoams, reactive thinners, plasticisers,antioxidants and light stabilisers.

As mentioned above, the novel compositions can be used as synergisticmixtures in combination with an accelerator of formulae M⁺X⁻ or M²⁺X⁻ ₂,wherein M⁺ and M^(n+) are an alkali metal ion or alkaline earth metalion, and X⁻ is any inorganic and/or organic anion, provided that theseaccelerators are soluble in the composition.

Such metal salt accelerators are known, inter alia, from EP-A-0 471 988,where they are proposed for accelerating the curing of epoxy resinsystems.

These accelerators may also be used in a 10-90% blend with polyetherpolyol-containing polyamines, such as the commercially available®Jeffamines of the ED/D- or T-type [supplied by Texaco Chemical Co.].Polyalkylene oxide is typically polyethylene oxide or polypropyleneoxide.

Preferred synergistic mixtures are those, wherein the alkali metalcation or alkaline earth metal cation is lithium or magnesium and/orcalcium, and the anion is X⁻ perchlorate, nitrate, laurylsulfate,acetate or iodide.

Very particularly preferred synergistic mixtures are those, wherein thealkali metal ion is Li⁺, the alkaline earth metal cation M²⁺ is calciumor magnesium, and the anion X⁻ is nitrate or perchlorate. M²⁺ isparticularly preferably calcium, and X⁻ is particularly preferablynitrate.

The metal salt accelerators are normally used in a concentration from0.1 to 10% by weight, preferably from 1 to 6% by weight, based on thesolids content of the polyamine hardener of formula I.

It is also possible to use 10 to 90% blends with ®Jeffamines of theED/D- or T-types or similar polyether polyols, preferably a 50% blendwith ®Jeffamine ED 600.

In addition to shortening the drying time, these metal salt acceleratorscan also have a favourable influence on the surface aspect, e.g. thegloss.

The preparation of the novel compositions can be carried out inconventional manner, typically by mixing the components of thecompositions by manual stirring or by stirring with known mixing unitsor dispersion aids (stirrers, kneaders, rolls, ball mills, tootheddisks, and the like).

The novel compositions are suitable, for example, for the preparation ofmatrix systems, laminates, paints, primers, coatings, finishings,fillers, knife fillers, sealing and injection compounds, immersionresins and casting resins, adhesives, and the like, as well as for themodification of concretes, mortars, and the like, and/or as adhesionpromoters on concretes, plastic materials, woods, natural and syntheticfibres, papers, and the like. They are particularly suitable for thepreparation of moulded articles and coatings.

Application of the novel compositions is conveniently carried out in thetemperature range from −5 to 200° C., preferably from 5 to 120° C. Thecure can be carried out in per se known manner in one or several steps.It is usually carried out at ambient temperature or by heating thecomposition to temperatures in the range from e.g. 30 to 120° C.,particularly preferably from 35 to 100° C. Owing to the mentionedexcellent properties of the novel compositions, a very wide range ofdifferent performance problems can be solved.

Accordingly, the invention also relates to crosslinked productsobtainable by curing the novel compositions.

The invention is illustrated by the following Examples wherein theabbreviations listed below are used:

EEW epoxy equivalent weight, i.e. the amount of a resin or reactionproduct comprising 1 mol of epoxy groups. EEW (prod.) epoxy equivalentweight of the product obtained. HAV_((≈NH) ⁺ _(-active)) amine-hydrogenequivalent weight, i.e. the amount of an amine or amine hardenercomprising 1 mol of NH₂ groups, based on the solids content of thehardener formulation. M_(m) average molecular weight Et ethyl IPDisophoronediamine = 1-amino-3-aminoethyl-3,5,5-trimethylcyclo-hexaneMXDA meta-xylylenediamine

EXPERIMENTAL PART Preparation of the Polyether Polyol/polyepoxyIntermediates in Accordance with Formula A and Their Modification(Examples 5 and 6)

General Processing Instructions

A specific amount of a polyether polyol and a polyepoxy compound isdissolved, with vigourous stirring, in an inert gas atmosphere. Themixture is heated to a temperature of 100° C. in the vessel and chargedwith a specific amount of a BF₃.EtNH₂ catalyst (see mol amounts in theExamples). The temperature in the vessel is elevated, with vigorousstirring, to the range from 120 to 180° C. and the reaction mixture iskept at this temperature until the desired epoxy value of the product isobtained.

Example 1:

0.3 mol of polyethylene oxide (M_(m)=1000)

1.3 mol of diglycidyl ether of bisphenol F (EEW=160 g/mol)

11.5 mmol of BF₃.EtNH₂

T=130° C., t=3 h, EEW (prod.)=340 g/equiv. of epoxy

Example 2:

0.3 mol of polyethylene oxide (M_(m)=1000)

1.3 mol of diglycidyl ether of bisphenol A (EEW=185 g/mol)

11.5 mmol of BF₃.EtNH₂

T=130° C., t=2.5 h, EEW (prod.)=381 g/equiv. of epoxy

Example 3:

0.3 mol of polyethylene oxide (M_(m)=1000)

0.78 mol of diglycidyl ether of bisphenol A (EEW=185 g/mol)

0.52 mol of diglycidyl ether of bisphenol F (EEW=160 g/mol)

17.7 mmol of BF₃.EtNH₂

T=130° C., t=3 h, EEW (prod.)=375 g/equiv. of epoxy

Example 4:

0.3 mol of polyethylene oxide (M_(m)=1000)

1.3 mol of diglycidyl ether of bisphenol A/F (6:4, EEW=175 g/mol)

11.5 mmol of BF₃.EtNH₂

T=130° C., t=3 h, EEW (prod.)=366 g/equiv. of epoxy

Example 5:

Modification (functionalisation) of the intermediate obtained accordingto Example 4 with diethylene glycol monoethyl ether(ethylcarbitol):

product of Example 4 (EEW=366 g/equiv. of epoxy)

+0.2 mol of ethylcarbitol

T=130° C., t=1 h, EEW (prod.)=430 g/equiv. of epoxy.

The product corresponds to a modified component b), as mentioned at theoutset.

Example 6:

Modification of the intermediate obtained in accordance with Example 4with di-n-butylamine:

Product of Example 4 (EEW=373 g/equiv. of epoxy)

+0.2 mol of di-n-butylamine

T=130° C., t=5 h, EEW (prod.)=414 g/equiv. of epoxy

Example 7:

0.48 mol of polyethylene oxide (M_(m)=1000)

0.48 mol of triblock copolymer PEO-PPO-PEO

(®Pluronics PE 4300: M_(m)=1700)

2.5 mol of diglycidyl ether of bisphenol A (EEW=185 g/mol)

1.6 mol of diglycidyl ether of bisphenol F (EEW=160 g/mol)

17.7 mmol of BF₃.EtNH₂

T=130° C., t=3.5 h, EEW (prod.)=400 g/equiv. of epoxy

PEO means: polyethylene oxide

PPO means: polypropylene oxide

Example 8:

0.77 mol of polyethylene oxide (M_(m)=1000)

0.19 mol of ABA triblock copolymer PEO-PPO-PEO

(®Pluronics PE 3100: M_(m)=1100)

2.5 mol of diglycidyl ether of bisphenol A (EEW=185 g/mol)

1.6 mol of diglycidyl ether of bisphenol F (EEW=160 g/mol)

17.7 mmol of BF₃.EtNH₂

T=130° C., t=3.5 h, EEW (prod.)=375 g/equiv. of epoxy

Example 9:

0.3 mol of polyethylene oxide (M_(m)=1000)

2.7 mol of novolak polyglycidyl ether of bisphenol F

[EPN 1179: (EEW=170 g/mol)]

9 mmol of BF₃.EtNH₂

T=155° C., t=4.5 h, EEW (prod.)=365 g/equiv. of epoxy

Example 10:

0.3 mol of polyethylene oxide (M_(m)=1000)

2.0 mol of novolak polyglycidyl ether of bisphenol F

[EPN 1179: (EEW=170 g/mol)]

13 mmol of BF₃.EtNH₂

T=150° C., t=2.5 h, EEW (prod.)=495 g/equiv. of epoxy

Preparation of the Novel Polyamine Adduct Hardener of Formula I

General Processing Instructions for Liquid Resin Adducts

A specific amount (based on the intermediate of formula A) of1,2-diaminocyclohexane or 1,3-diamino-4-methylcyclohexane (as indicatedin the Examples) is placed in a reactor in an inert gas atmosphere at abath temperature of 40° C. and then, with stirring, the intermediate(described in the Examples) is added in the respective amounts such thatthe exothermic reaction is kept at 40-50° C. The reaction mixture iskept at this temperature for 1-2 hours and subsequently the temperaturein the reactor is raised for 1 hour to 100° C. After cooling to 40-70°C., the product is adjusted with a specific amount of water to a solidscontent of 70-80% by weight (see Examples 11 to 19).

Example 11:

30 g of the intermediate of Example 1

13 g (0.11 mol) of 1,2-diaminocyclohexane

10.75 g of water

solids content=80% by weight

NH⁺-active=146.5 g/equiv. of NH⁺

viscosity: 12800 mPa·s

Example 12:

35.5 g of the intermediate of Example 2

15 g (0.13 mol) of 1,2-diaminocyclohexane

12.7 g of water

solids content=80% by weight

NH⁺-active=146 g/equiv. of NH⁺

viscosity: 37100 mPa·s

Example 13:

193 g of the intermediate of Example 3

63 g (0.55 mol) of 1,2-diaminocyclohexane

64 g of water

solids content=80% by weight

NH⁺-active=190 g/equiv. of NH⁺

viscosity: 60000 mPa·s

Example 14:

163 g of the intermediate of Example 3

93 g (0.8 mol) of 1,2-diaminocyclohexane

63.9 g of water

solids content=80% by weight

NH⁺-active=113 g/equiv. of NH⁺

viscosity: 10000 mPa·s

Example 15:

35 g of the intermediate of Example 4

16.3 g (0.13 mol) of 1,3-diamino-4-methylcyclohexane

12.8 g of water

solids content=80% by weight

NH⁺-active=151 g/equiv. of NH⁺

viscosity: 20000 mPa·s

Example 16:

50 g of the intermediate of Example 5

22 g (0.19 mol) of 1,2-diaminocyclohexane

18 g of water

solids content=80% by weight

NH⁺-active=140 g/equiv. of NH⁺

viscosity: 15000 mPa·s

Example 17:

50 g of the intermediate of Example 6

20.1 g (0.176 mol) of 1,2-diaminocyclohexane

17.5 g of water

solids content=80% by weight

NH⁺-active=150 g/equiv. of NH⁺

viscosity: 19000 mPa·s

Example 18:

35.5 g of the intermediate of Example 7

15.5 g (0.14 mol) of 1,2-diaminocyclohexane

12.75 g of water

solids content=80% by weight

NH⁺-active=140 g/equiv. of NH⁺

viscosity: 17300 mPa·s

Example 19:

35 g of the intermediate of Example 8

15 g (0.14 mol) of 1,2-diaminocyclohexane

12.5 g of water

solids content=80% by weight

NH⁺-active=144.5 g/equiv. of NH⁺

viscosity: 19200 mPa·s

Modification of the novel adducts [formula I] by the addition of asecond more reactive polyamine [component c)] according to per se knownmethods after the reaction of the epoxy-containing intermediate with1,2-diaminocyclohexane is complete:

Example 20:

35 g of the intermediate of Example 4 (EEW=386 g/mol of epoxy)

9.6 g (0.084 mol) of 1,2-diaminocyclohexane

8.25 g (0.048 mol) of isophoronediamine [component c)]

13.2 g of water

solids content=80% by weight

NH⁺-active=153 g/equiv. of NH⁺

viscosity: 29400 mPa·s

Example 21:

35 g of the intermediate of Example 8 (EEW=375 g/mol of epoxy)

11.5 g (0.10 mol) of 1,2-diaminocyclohexane

3.95 g (0.024 mol) of meta-xylylenediamine [component c)]

12.6 g of water

solids content=80% by weight

NH⁺-active=148 g/equiv. of NH⁺

viscosity: 36000 mPa·s

Example 22:

35 g of the intermediate of Example 8 (EEW=375 g/mol of epoxy)

8.14 g (0.07 mol) of 1,2-diaminocyclohexane

6.17 g (0.053 mol) of 2-methyl-1,5-diaminopentane [component c)]

12.3 g of water

solids content=80% by weight

NH⁺-active=152 g/equiv. of NH⁺

viscosity: 33900 mPa·s

Example 22-I:

35 g of the intermediate of Example 8 (EEW=386 g/mol of epoxy)

10.11 g (0.088 mol) of 1,2-diaminocyclohexane

6.44 g (0.042 mol) of 2,5(2,6)-bis(aminomethyl)bicyclo(2.2.1)heptane

[NBDA; component c)]

12.88 g of water

solids content=80% by weight

NH⁺-active=120 g/equiv. of NH⁺

viscosity: 29000 mPa·s

General Processing Instructions for Epoxy Novolak Adducts [Formula I,Wherein B=Formula V]

A specific amount of diaminocyclohexane is placed in a reactor in aninert gas atmosphere at a bath temperature of 90° C. and then, withstirring, the intermediate of Example 9 or 10 dissolved in toluene isadded, such that the exothermic reaction is kept at a temperature of 90°C. in the vessel. The reaction mixture is kept at this temperature for 2hours and then the temperature in the vessel is slowly raised to 200°C., all the while distilling off the solvent toluene. Upon reaching atemperature of 150° C. in the vessel, a sufficient vacuum is applied andexcess diaminocyclohexane is removed from the reaction mixture bydistillation. After cooling the reaction mixture to 60° C., the productremaining in the reactor is diluted with a specific amount of water to asolids content of 70-80% by weight.

Example 23:

48 g of the intermediate of Example 9

dissolved in 12 g of toluene

15 g (0.13 mol) of 1,2-diaminocyclohexane (excess 75 g)

17 g of water

solids content=78% by weight

NH⁺-active=205 g/equiv. of NH⁺

viscosity: 44800 mPa·s

Example 24:

48 g of the intermediate of Example 10 dissolved in 12 g of toluene

12 g (0.1 mol) of 1,2-diaminocyclohexane (excess 60 g)

26 g of water

solids content=70% by weight

NH⁺-active=265 g/equiv. of NH⁺

viscosity: 48600 mPa·s

General Processing Instructions for Polyamine Hardeners Comprising anAccelerator

A specific amount (based on the intermediate) of diaminocyclohexane isplaced in a reactor in an inert gas atmosphere at a bath temperature of40° C. and then the respective intermediate (described in the Examples1-10) is added such that the exothermic reaction is kept at 40-500° C.The reaction mixture is kept at this temperature for 1-2 hours and thenthe temperature in the vessel is raised for 1 hour to 100° C. Aftercooling to 50° C., the product is charged with the metal salt dissolvedin water (0.1-10% by weight, based on the solids of the adduct). Thenovel synergistic mixture is adjusted to a solids content of 70-80% byweight in a specific amount of water.

Example 25:

35.5 g of the intermediate of Example 3

16 g (0.14 mol) of 1,2-diaminocyclohexane

2.06 g of LINO₃ dissolved in 13.4 g of water

solids content=80% by weight

NH⁺-active=140 g/equiv. of NH⁺

Example 26:

35.5 g of the intermediate of Example 3

16 g (0.14 mol) of 1,2-diaminocyclohexane

1.54 g of Ca(NO₃)₂ dissolved in 13 g of water

solids content=80% by weight

NH⁺-active=140 g/equiv. of NH⁺

Application Examples

General Processing Instructions for the Preparation, Application andTesting of Coatings Based on the Novel Compositions

100 g of a liquid epoxy resin based on a mixture of bisphenol A andbisphenol F having an EEW of about 180 (Table 1) or 100 g of an emulsionbased on a solid epoxy resin based on bisphenol A (EEW 500-540), solidscontent of the emulsion about 55% by weight (Table 2), are thoroughlymixed with x g (exact amounts see Tables 1 and 2) of one of the novelpolyamine hardeners. If required, the mixture is diluted with deionisedwater to achieve a solids content of 55-60% by weight. Using a filmdrawing frame or a knife coater, the paint formulation so obtained iscoated on a suitable substrate (e.g. glass plates, metal plates) at awet film thickness of about 200 μm. The coatings so obtained are fullycured at room temperature. The paint properties of the coatings soobtained are indicated in Tables 1 (liquid resin) and 2 (solid resinemulsion).

“Working life” will be understood to denote the period of time after theepoxy resin and the polyamine hardener are mixed, during which the glossof a coating applied does not diminish more than 10%.

“Dust dry time” will be understood to denote the period of time duringwhich sand strewn on the coating (grain size: about 0.2 mm) adheres.

TABLE 1 Paint properties of coatings based on the novel polyaminehardeners and a liquid epoxy resin ( ® Araidit PY 340-2, EEW about 180)formulation No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 16-I polyaminehardener acc. 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 22-I tosynthesis Example No. amount of poly- 82 82 107 64 82 75 82 82 79 82 8282 130 147 79 79 80 amine hardener [g] working life [h]¹⁾ 5 >6 7 8 3 3 67 7 5 3.5 5 5 3 5 5 3.5 dust-dry time [h]²⁾ 10 8 11 11 6.5 11 12 9 8 8 611 3.7 10 3 1 5.5 film forming o.k. o.k. o.k. o.k. o.k. o.k. o.k. o.k.o.k. o.k. o.k. o.k. o.k. o.k. o.k. o.k. o.k. flow o.k. o.k. o.k. o.k.o.k. o.k. o.k. o.k. o.k. o.k. o.k. o.k. o.k. o.k. o.k. o.k. o.k.pendulum hardness 327 329 320 314 312 280 320 302 320 325 335 288 315257 349 340 320 (Persoz) after 7 days [s]³⁾ Film forming o.k. means thatthe result of a visual assessment is okay. Flow o.k. means that theresult of a visual assessment is okay. ¹⁾Reflexion measurement on BYKcontrast cards; reflexion angle 60° C., decrease of about 10%.²⁾According to Dr. Landolt (Chemical and Physical Test Methods for EpoxyResin Systems; S.15; Ciba; Dec.1991). ³⁾According to ISO Norm 1552/73.

TABLE 2 Paint properties of coatings based on the novel polyaminehardeners and an emulsion based on a solid epoxy resin ( ® Araldit PZ3961 EEW 500-540) formulation No. 17 18 19 20 21 22 23 24 25 26 27 28 2930 31 32 polyamine hardener 11 12 13 14 15 16 17 18 19 20 21 22 23 24 2526 acc. to synthesis Example No. amount of poly- 14.7 14.7 20 12 16.513.5 14.7 16.7 15.3 14.5 14.5 14.5 23 24 14.5 14.5 amine hardener [g]working life [h] 4 4 4 3.5 2.75 3 4 4 4 2.5 2.5 2.5 4 4 4 4 dust-drytime [h] 2.5 2.5 2.5 2 2.5 3 2 2 2.5 1.5 1.25 1.5 3.5 3 0.7 0.5 filmforming o.k. o.k. o.k. o.k. o.k. o.k. o.k. o.k. o.k. o.k. o.k. o.k. o.k.o.k. o.k. o.k. flow o.k. o.k. o.k. o.k. o.k. o.k. o.k. o.k. o.k. o.k.o.k. o.k. o.k. o.k. o.k. o.k. pendulum hardness 242 235 317 346 310 285280 272 285 282 285 270 275 100 305 244 (Persoz) after 14 days [s] Filmforming o.k. means that the result of a visual assessment is okay. Flowo.k. means that the result of a visual assessment is okay.

What is claimed is:
 1. A curable composition, comprising a) 10 to 90% byweight of at least one, optionally water-dilutable, water-emulsifiableor water-dispersible, epoxy resin having more than one epoxy group inthe molecule; b) 90 to 10% by weight of at least one polyamine adductwhich predominantly corresponds to the formula I and which is preparedfrom an adduct of formula A and a polyamine of formula XII,

wherein the sum of the percentages by weight of components a) and b) is100%; c) optionally, at least one further aliphatic, cycloaliphatic,aromatic/aliphatic, aromatic or heteroaromatic mono- or polyamine whichis unmodified or modified by adduction; and, d) optionally, at least onecustomary additive selected from the group consisting of extenders,fillers, reinforcing agents, pigments, pigment pastes, colourants, flameretardants, thixotropic agents, flow control agents, demoulding agents,antifoams, reactive thinners, plasticisers, antioxidants and lightstabilisers; wherein in formulae I, A and XII R¹ is independently of oneanother —H or —CH₃, R² is —H or C₁-C₁₂ alkyl, and p is 1, 2 or 3, theradicals B are each independently of one another a group of formulae II,III, IV, V, VI, VII, VIII, IX and X:

wherein X is >N— or —O—, R is —H or —CH₃, and q is an integer from 0 to10, m in formulae I and A, depending on the functionality of unit B, isan integer from 1 to 11, and n is an integer from 2 to 100, and r informulae VI and VII is an integer from 2 to
 20. 2. A curable compositionaccording to claim 1, wherein in formula I R² is —H or —CH₃, and p is 1,and m, depending on the functionality of unit B, is an integer from 1 to5, and n is an integer from 4 to
 25. 3. A curable composition accordingto claim 2, wherein in formula I R² is —H, and p is 1, and the freeamino groups are in the ortho-position to the other amino groups boundto the adduct of formula A, or R² is —CH₃, and p is 1, and the freeamino groups are in the meta-position to the other amino groups bound tothe adduct of formula A, the radicals B are independently of one anothera group of formulae II, III, IV and V

or of formula VI —O—(CH₂)_(r)—O—, wherein r is an integer from 2 to 10.4. A curable composition according to claim 3, wherein in formula I R²is —H, and p is 1, and the free amino groups are in the ortho-positionto the other amino groups bound to the adduct of formula A, wherein informula V q is 0 to 3, and r in formula VI is 4 or
 6. 5. A curablecomposition according to claim 1, wherein the adduct A is partiallymodified with a monoalkyl ether or a secondary amine.
 6. A curablecomposition according to claim 1, wherein an accelerator of formula M⁺X⁻or M²⁺X⁻ ₂ is used as additional component, wherein M⁺ or M²⁺ is analkali metal ion or an alkaline earth metal ion, and X⁻ is any inorganicand/or organic anion, which accelerator is soluble in the curablecomposition.
 7. A curable composition according to claim 6, wherein M⁺is Li⁺, and M²⁺ is Mg²⁺ or Ca²⁺, and X⁻ is ClO₄ ⁻, NO₃ ⁻, laurylsulfate,acetate or iodide.
 8. A curable composition according to claim 7,wherein M⁺ is Li⁺, and M²⁺ is Mg²⁺ or Ca²⁺, and X⁻ is ClO₄ ⁻ or NO₃ ⁻.9. A curable composition according to claim 8, wherein M²⁺ is Ca²⁺ andX⁻ is NO₃ ⁻.
 10. A curable composition according to claim 6, wherein theaccelerator is present in a 10 to 90% blend with at least onepolyalkylene oxide-containing polyamine.
 11. A curable compositionaccording to claim 10, wherein the polyamine is ®Jeffamine of the ED/D-or T-series.
 12. A curable composition according to claim 10, whereinthe accelerator is present in 50% blend with ®Jeffamine ED
 600. 13. Themoulded articles and coatings obtained by curing the compositionaccording to claim 1.